Source reagent compositions for CVD formation of gate dielectric thin films using amide precursors and method of using same

ABSTRACT

A CVD Method of forming gate dielectric thin films on a substrate using metalloamide compounds of the formula M(NR 1 R 2 ) x , or  
                 
 
     wherein M is Zr, Hf, Y, La, Lanthanide series elements, Ta, Ti, or Al; N is nitrogen; each of R 1  and R 2  is same or different and is independently selected from H, aryl, perfluoroaryl, C 1 -C 8  alkyl, C 1 -C 8  perfluoroalkyl, alkylsilyl; and x is the oxidation state on metal M; and an aminosilane compound of the formula 
     H x SiA y (NR 1 R 2 ) 4−x−y   
     or  
                 
 
     wherein H is hydrogen; x is from 0 to 3; Si is silicon; A is a halogen; Y is from 0 to 3; N is nitrogen; each of R 1  and R 2  is same or different and is independently selected from the group consisting of H, aryl, perfluoroaryl, C 1 -C 8  alkyl, and C 1 -C 8  perfluoroalkyl; and n is from 1-6. By comparison with the standard SiO 2  gate dielectric materials, these gate dielectric materials provide low levels of carbon and halide impurity.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to chemical vapor depositionprocesses and source reagent compositions useful for the formation ofsingle component or multicomponent high dielectric constant thin filmsthat may be used in semiconductor materials.

[0003] 2. Description of the Related Art

[0004] Semiconductor devices such as field effect transistors (FET) andmetal oxide semiconductor capacitors (MOS-caps) are common in theelectronics industry. Such devices may be formed with dimensions thatenable thousands or even millions of devices to be formed on asingle-crystal substrate and interconnected to perform useful functionsin an integrated circuit such as a microprocessor.

[0005] The general structure and operation of a field effect transistoris as follows. With reference to FIG. 1, a simplified field effecttransistor is shown in cross-section. In a field effect transistor aportion of the substrate (or epi-layer) 100 near the surface isdesignated as the channel 120 during processing. Channel 120 iselectrically connected to source 140 and drain 160, such that when avoltage difference exists between source 140 and drain 160, current willtend to flow through channel 120. The semiconducting characteristics ofchannel 120 are altered such that its resistivity may be controlled bythe voltage applied to gate 200, a conductive layer overlying channel120.Thus by changing the voltage on gate 200, more or less current canbe made to flow through channel 120. Gate 200 and channel 120 areseparated by gate dielectric 180; the gate dielectric is insulating,such that between gate 200 and channel 120 the current flow duringoperation is small compared to the source to drain current (although“tunneling” current is observed with thin dielectrics.) However, thegate dielectric allows the gate voltage to induce an electric field inchannel 120, giving rise to the name “field effect transistor.” Thegeneral structure of a MOS-cap can be visualized as layers 200, 180 and120 of FIG. 1 without the source and drain. The MOS-cap functions as acapacitor.

[0006] SiO₂ represents the highest quality gate dielectric material 180so far developed in silicon technology with low defects and low surfacestate density. One important advantage of SiO₂ is that it may be grownfrom the silicon substrate at elevated temperatures in an oxidizingenvironment. It is well known in the art, that thermally grown oxidestend to have fewer defects, (i.e. pinholes), than deposited materials.Thus, SiO₂ has persisted as the dielectric material in most silicondevice structures.

[0007] Generally, integrated circuit performance and density may beenhanced by decreasing the size of the individual semiconductor deviceson a chip. Unfortunately, field effect semiconductor devices produce anoutput signal that is proportional to the length of the channel, suchthat scaling reduces their output. This effect has generally beencompensated for by decreasing the thickness of gate dielectric 180, thusbringing the gate in closer proximity to the channel and enhancing thefield effect.

[0008] As devices have scaled to smaller and smaller dimensions, thegate dielectric thickness has continued to shrink. Although furtherscaling of devices is still possible, scaling of the gate dielectricthickness has almost reached its practical limit with the conventionalgate dielectric materials: silicon dioxide, silicon oxy-nitride andsilicon nitride. Further scaling of silicon dioxide gate dielectricthickness will involve problems such as: extremely thin layers allowingfor large leakage currents due to direct tunneling through the oxide.Because such layers are formed literally from a few atomic layers, exactprocess control is required to repeatably produce such layers.Uniformity of coverage is also critical because device parameters maychange dramatically based on the presence or absence of even a singlemonolayer of dielectric material. Finally, such thin layers form poordiffusion barriers to impurities and dopants.

[0009] Consequently, there is a need in the art for alternativedielectric materials, which can be formed in a thicker, layer thansilicon dioxide and yet still produce the same field effect performance.This performance is often expressed as “equivalent oxide thickness”(EOT). Although the alternative material layer may be thick, it has theequivalent effect of a much thinner layer of silicon dioxide (commonlycalled simply “oxide”). In order to have a physically thick layer with alow EOT, the dielectric constant of the insulating material must beincreased. Many, if not most, of the attractive alternatives forachieving low equivalent oxide thicknesses are metal oxides, such astantalum pentoxide, titanium dioxide, barium strontium titanate andother suitable thin films.

[0010] However, the formation of such metal oxides as gate dielectricshas been found to be problematic. At typical metal oxide depositiontemperatures, the oxygen co-reactant or oxygen-containing precursortends to oxidize the silicon substrate, producing a lower dielectricconstant oxide layer at the interface between the substrate and thehigher dielectric constant, gate dielectric material. It could be thatthe transition metal oxide acts as a catalytic source of activatedoxygen, that the precursor molecules increase the oxygen activity orthat oxygen from the precursor is incorporated in the growing oxidefilm. Whatever the cause, the presence of this interfacial oxide layerincreases the effective oxide thickness, reducing the effectiveness ofthe alternative gate dielectric material. The existence of theinterfacial oxide layer places a severe constraint on the performance ofan alternative dielectric field effect device and therefore, isunacceptable.

[0011] The use of metal oxide and metal oxy-nitride thin filmscomprising Zr, Hf, Y, La, Lanthanide series elements, Ta, Ti and/or Aland silicates of these metal oxides and metal oxy-nitrides are regardedas potential material replacements of the SiO₂ gate oxides, (i.e., U.S.Pat. Nos. 6,159,855 and 6,013,553). However, to ensure a high integrityinterface between the silicon and the gate dielectric film these filmsmust be deposited at relatively low temperatures.

[0012] The source reagents and methodology employed to form such gatedielectric thin films are extremely critical for the provision of a gatestructure having satisfactory electrical performance characteristics inthe product device. Specifically, the source reagents and methodologymust permit the gate dielectric thin film to form on a clean siliconsurface, without the occurrence of side reactions producingpredominantly silicon dioxide (SiO₂), locally doped SiO₂ and/or otherimpurities, that lower the dielectric constant and compromise theperformance of the product microelectronic device. Further, the absenceof carbon contamination is highly desirable.

[0013] Impurities that are known to lower the dielectric constant and/orincrease leakage include among others, carbon and halides, such asfluorine and chlorine. Carbon incorporation into the dielectric thinfilm would degrade leakage, dielectric constant, and overall electricalperformance of the thin film. In contrast, nitrogen incorporation mayexhibit some beneficial properties on the dielectric thin film.

[0014] Chemical vapor deposition (CVD) is the thin film depositionmethod of choice for high-density, large-scale fabrication ofmicroelectronic device structures, and the semiconductor manufacturingindustry has extensive expertise in its use. Metalorganic CVD (MOCVD)and more particularly atomic layer MOCVD (ALCVD) are particularlyadvantageous processes because they allow for lower depositiontemperatures and stricter control of the stoichiometry and thickness ofthe formed layer.

[0015] In the formation of gate dielectrics and other semiconductormanufacturing applications it is essential to control the composition ofthe deposited thin film. The molar ratio(s) of the different elements inthe thin film typically corresponds very closely to a predeterminedvalue. Therefore, it is very important to select a precursor deliverysystem that allows for strict control of the precursors delivered intothe CVD chamber. Precursor delivery systems are well known in the art ofCVD, (i.e., U.S. Pat. No. 5,820,678, entitled “Solid Source MOCVDSystem” describes the bubbler delivery approach and U.S. Pat. No.5,204,314, entitled “Method for Delivering an Involatile Reagent inVapor Form to a CVD Reactor,” and U.S. Pat. No. 5,536,323, entitled“Apparatus for Flash Vaporization Delivery of Reagents,” describe theliquid delivery, flash vaporization approach).

[0016] The source reagents must be thermally stable to avoid prematuredecomposition of such source reagents before they reach the CVD reactionchamber during the CVD process. Premature decomposition of sourcereagents not only results in undesirable accumulation of side productsthat will clog fluid flow conduits of the CVD apparatus, but also causesundesirable variations in composition of the deposited gate dielectricthin film. Further, particle formation can result in deleterious yieldsin device fabrication.

[0017] Further, Zr, Hf, Y, La, Lanthanide series elements, Ta, Ti, Aland and/or silicon source reagents have to be chemically compatible withother source reagents used in the CVD process. “Chemically compatible”means that the source reagents will not undergo, undesirable sidereactions with other co-deposited source reagents, and/or deleteriousligand exchange reactions that may alter the precursor properties, suchas transport behavior, incorporation rates and film stoichiometries.

[0018] Finally, Zr, Hf, Y, La, Lanthanide series elements, Ta, Ti, Aland/or silicon source reagents selected for MOCVD of dielectric thinfilms must be able to maintain their chemical identity over time whendissolved or suspended in organic solvents or used in conventionalbubblers. Any change in chemical identity of source reagents in thesolvent medium is deleterious since it impairs the ability of the CVDprocess to achieve repeatable delivery and film growth.

[0019] There is a continuing need in the art to provide improved Zr, Hf,Y, La, Lanthanide series elements, Ta, Ti, Al and/or silicon sourcereagents suitable for high efficiency CVD processes, for fabricatingcorresponding high quality gate dielectric, thin films.

[0020] Further, there is a need in the art for oxygen-free Zr, Hf, Y,La, Lanthanide series elements, Ta, Ti, Al and/or silicon sourcereagents suitable for high efficiency CVD processes, for fabricatingcorresponding high quality gate dielectric thin films for the reasons asstated hereinabove.

[0021] Therefore, it is an object of this invention to provide CVDprecursors and CVD processes to deposit high dielectric constant thinfilms, having minimum carbon and halide incorporation and when depositedon a silicon substrate, minimal SiO₂ interlayer.

SUMMARY OF THE INVENTION

[0022] The present invention broadly relates to a precursor compositionhaving utility for forming dielectric thin films such as gatedielectric, high dielectric constant metal oxides, and ferroelectricmetal oxides and to a low temperature chemical vapor deposition (CVD)process for deposition of such dielectric thin films utilizing suchcompositions.

[0023] As used herein the term “thin film” refers to a material layerhaving a thickness of less than about 1000 microns.

[0024] In one aspect, the present invention relates to a CVD precursorcomposition for forming a thin film dielectric on a substrate, suchprecursor composition including at least one source reagent compoundselected from the group consisting of:

M(NR¹R²)_(x);

[0025] and

[0026] wherein M is selected from the group consisting of: Zr, Hf, Y,La, Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹and R² is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6.

[0027] As used herein, the term “lanthanides series elements” refers tothe 14 elements following lanthanum in the Periodic Table, viz., cerium,praseodymium, neodymium, promethium, samarium, europium, gadolinium,terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

[0028] In another aspect, the present invention relates to a CVDprecursor composition for forming a thin film dielectric on a substrate,such precursor composition including at least one source reagentcompound selected from the group consisting of:

H_(x)SiA_(y)(NR¹R²)_(4−x−y);

[0029] and

[0030] wherein H is hydrogen; x is from 0 to 3; Si is silicon; A is ahalogen; Y is from 0 to 3; N is nitrogen; each of R¹ and R² is same ordifferent and is independently selected from the group consisting of H,aryl, perfluoroaryl, C₁-C₈ alkyl, and C₁-C₈ perfluoroalkyl; and n isfrom 1-6.

[0031] In a further aspect, the present invention relates to a CVDprecursor composition for forming a thin film dielectric on a substrate,such precursor composition including a vapor source reagent selectedfrom the group consisting of:

M(NR¹R²)_(x);

[0032] and

[0033] wherein M is selected from the group consisting of: Zr, Hf, Y,La, Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹and R² is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6.

[0034] In a further aspect, the present invention relates to a CVDprecursor composition for forming a thin film dielectric on a substrate,such precursor composition including a vapor source reagent mixtureincluding a metalloamide source reagent compound selected from the groupconsisting of:

M(NR¹R²)_(x);

[0035] and

[0036] wherein M is selected from the group consisting of: Zr, Hf, Y,La, Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹and R² is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6;and

[0037] an aminosilane source reagent compound selected from the groupconsisting of:

H_(x)SiA_(y)(NR¹R²)_(4−x−y);

[0038] and

[0039] wherein H is hydrogen; x is from 0 to 3; Si is silicon; A is ahalogen; Y is from 0 to 3; N is nitrogen; each of R¹ and R² is same ordifferent and is independently selected from the group consisting of H,aryl, perfluoroaryl, C₁-C₈ alkyl, and C₁-C₈ perfluoroalkyl; and n isfrom 1-6.

[0040] In a further aspect, the present invention relates to a CVDsingle source precursor composition for forming a silicate thin filmdielectric on a substrate, the precursor composition comprising a vaporsource mixture comprising at least one metalloamide vapor source reagentselected from the group consisting of:

M(NR¹R₂)_(x);

[0041] and

[0042] wherein M is selected from the group consisting of: Zr, Hf, Y,La, Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹and R² is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6;and

H_(x)SiA_(y)(NR¹R²)_(4−x−y);

[0043] and

[0044] wherein H is hydrogen; x is from 0 to 3; Si is silicon; A is ahalogen; Y is from 0 to 3; N is nitrogen; each of R¹ and R² is same ordifferent and is independently selected from the group consisting of H,aryl, perfluoroaryl, C₁-C₈ alkyl, and C₁-C8 perfluoroalkyl; and n isfrom 1-6.

[0045] Another aspect of the present invention relates to a CVDprecursor composition comprising a metalloamide source reagent compoundand/or an aminosilane source reagent compound as described hereinabove,and a solvent medium in which the source reagent compound(s) is solubleor suspendable.

[0046] In another aspect, the invention relates to formation of adielectric thin film on a substrate from a precursor compositioncomprising a metalloamide source reagent compound, comprising vaporizingthe precursor composition to form a vaporized precursor, and contactingthe vaporized precursor with the substrate to deposit a metal-containingfilm thereon.

[0047] In a further aspect, the present invention relates to a CVDmethod of forming a dielectric thin film on a substrate, comprising thesteps of:

[0048] vaporizing a precursor composition comprising at least onemetalloamide source reagent compound to form a source reagent precursorvapor;

[0049] transporting the source reagent precursor vapor into a chemicalvapor deposition zone, optionally using a carrier gas;

[0050] contacting the source reagent precursor vapor with a substrate insaid chemical vapor deposition zone at elevated temperature to deposit adielectric thin film on the substrate.

[0051] In a further aspect, the present invention relates to a CVDmethod of forming a dielectric thin film on a substrate, comprising thesteps of:

[0052] vaporizing a multicomponent precursor composition mixturecomprising at least one metalloamide source reagent compound and atleast one aminosilane source reagent compound, to form a source reagentprecursor vapor;

[0053] transporting the source reagent precursor vapor into a chemicalvapor deposition zone, optionally using a carrier gas;

[0054] contacting the source reagent precursor vapor with a substrate insaid chemical vapor deposition zone at elevated temperature, to deposita dielectric thin film on the substrate.

[0055] In still a further embodiment, the present invention relates to amethod of making a gate dielectric and a gate electrode comprising thesteps of:

[0056] vaporizing a precursor composition comprising at least onemetalloamide source reagent compound to form a source reagent precursorvapor;

[0057] transporting the source reagent precursor vapor into a chemicalvapor deposition zone, optionally using a carrier gas;

[0058] contacting the source reagent precursor vapor with a substrate insaid chemical vapor deposition zone at elevated temperature to deposit adielectric thin film on the substrate;

[0059] vaporizing a precursor composition comprising at least onemetalloamide source reagent compound to form a source reagent precursorvapor;

[0060] transporting the source reagent precursor vapor into a chemicalvapor deposition zone, optionally using a carrier gas;

[0061] contacting the source reagent precursor vapor with a substrate,comprising the dielectric thin film, in said chemical vapor depositionzone at elevated temperature to deposit a gate conducting thin film onthe dielectric thin film.

[0062] In yet a farther embodiment the present invention relates to adielectric thin film formed by a method as described hereinabove.

[0063] Other aspects, features, and embodiments of the invention will bemore fully apparent from the ensuing disclosure and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0064]FIG. 1 is a cross-sectional view of a typical prior art integratedcircuit field effect transistor.

[0065] FIGS. 2A and FIG. 2B show a pressure temperature matrix forHf(N(C₂H₅)₂)₄ (Tetrakis(diethyl-amino)hafnium) and Hf(N(CH₃)₂)₄(Tetrakis(dimethyl-amino)hafnium) in N₂O.

[0066]FIG. 3 shows the growth rate of hafnia films in differentoxidizing ambients at 8 Torr and 550° C.

[0067]FIGS. 4A and 4B show growth rate over process space forHf(N(C₂H₅)₂)₄ (Tetrakis(diethyl-amino)hafnium) and Hf(N(CH₃)₂)₄(Tetrakis(dimethyl-amino)hafnium.

[0068]FIG. 5 shows RMS roughness as measured by AFM over 1×1 μm areas ofHf(N(C₂H₅)₂)₄ (Tetrakis(diethyl-amino)hafnium) and Hf(N(CH₃)₂)₄(Tetrakis(dimethyl-amino)hafnium) thin films.

[0069]FIG. 6 shows index of refraction measurements as a function ofprocess conditions for Hf(N(CH₃)₂)₄ (Tetrakis(dimethyl-amino)hafnium)thin films.

[0070]FIGS. 7A and 7B show a limited pressure-temperature matrix forSi(N(C₂H₅)₂)₂Cl₂ (Bis(diethyl-amino)dichlorosilane) and Si(N(CH₃)₂)₃Cl(Tris(dimethyl-amino)chlorosilane in N₂O.

[0071]FIG. 8 shows the growth rate of silica from Si(N(C₂H₅)₂)₂Cl₂(Bis(diethyl-amino)dichlorosilane) in N₂O ambient.

[0072]FIG. 9 shows the growth rate of silica from Si(N(CH₃)₂)₃Cl(Tris(dimethyl-amino)chlorosilane in N₂O ambient.

[0073]FIG. 10 shows the growth rate of SiO₂ under a HfO₂ film with nosilicon precursor present.

[0074]FIG. 11 shows the growth rate of SiO₂ from Si(N(C₂H₅)₂)₂Cl₂(Bis(diethyl-amino)dichlorosilane when co-deposited with HfO₂ fromHf(N(C₂H₅)₂)₄ (Tetrakis(diethyl-amino)hafnium in N₂O ambient.

DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS THEREOF

[0075] The disclosure of the following United States patents and patentapplications are hereby incorporated by reference in their respectiveentireties:

[0076] U.S. patent application Ser. No. 09/414,133 filed Oct. 7, 1999 inthe names of Thomas H. Baum, et al.;

[0077] U.S. patent application Ser. No. 09/012,679 filed Jan. 23, 1998in the names of Gautam Bhandari, et al., and issued Jan. 18, 2000 asU.S. Pat. No. 6,015,917;

[0078] U.S. patent application Ser. No. 08/979,465 filed Nov. 26, 1997in the names of Frank DiMeo, Jr., et al., and issued Oct. 26, 1999 asU.S. Pat. No. 5,972,430;

[0079] U.S. patent application No. 08/835,768 filed Apr. 8, 1997 in thenames of Thomas H. Baum, et al., and issued Jul. 6, 1999 as U.S. Pat.No. 5,919,522;

[0080] U.S. patent application Ser. No. 08/484,654 filed Jun. 7, 1995 inthe names of Robin A. Gardiner et al., and issued Aug. 29, 2000 as U.S.Pat. No. 6,110,529;

[0081] U.S. patent application Ser. No. 08/414,504 filed Mar. 31, 1995in the names of Robin A. Gardiner et al., and issued Oct. 13, 1998 asU.S. Pat. No. 5,820,664;

[0082] U.S. patent application Ser. No. 08/280,143 filed Jul. 25, 1994in the names of Peter S. Kirlin, et al., and issued Jul. 16, 1996 asU.S. Pat. No. 5,536,323;

[0083] U.S. patent application Ser. No. 07/927,134, filed Aug. 7, 1992in the same names;

[0084] U.S. patent application Ser. No. 07/807,807 filed Dec. 13, 1991in the names of Peter S. Kirlin, et al., and issued Apr. 20, 1993 asU.S. Pat. No. 5,204,314;

[0085] U.S. patent application Ser. No. 08/181,800 filed Jan. 15, 1994in the names of Peter S. Kirlin, et al., and issued Sep. 26, 1995 asU.S. Pat. No. 5,453,494;

[0086] U.S. patent application Ser. No. 07/918,141 filed Jul. 22, 1992in the names of Peter S. Kirlin, et al., and issued Jan. 18, 1994 asU.S. Pat. No. 5,280,012;

[0087] U.S. application Ser. No. 07/615,303 filed Nov. 19, 1990;

[0088] U.S. patent application Ser. No. 07/581,631 filed Sep. 12, 1990in the names of Peter S. Kirlin, et al., and issued Jul. 6, 1993 as U.S.Pat. No. 5,225,561.

[0089] U.S. patent application Ser. No. 07/549,389 filed Jul. 6, 1990 inthe names of Peter S. Kirlin, et al.

[0090] U.S. patent application Ser. No. 08/758,599 filed Nov. 27, 1996in the names of Jeffrey F. Roeder, et al., and issued Mar. 2, 1999 asU.S. Pat. No. 5,876,503.

[0091] The above-identified applications and patents variously describesource reagent compositions and their synthesis and formulation, as wellas CVD techniques including, liquid delivery chemical vapor deposition(LDCVD), and digital or atomic layer chemical vapor deposition (ALCVD)and provide background and assistive information with respect to thepractice of the present invention.

[0092] The metalloamide precursors of the present invention, whenutilized in a CVD process to deposit dielectric thin films on asubstrate, result in a dielectric thin film having very low levels ofcarbon and little or no halide impurity. Further, when the metalloamideprecursors of the present invention are used to deposit metal silicategate dielectric thin films, the thickness of the SiO₂ interlayer isminimal or absent and the dielectric constant of the thin film issubstantially higher than that of conventional thermal silicon.

[0093] Even after a high temperature anneal, the gate dielectric thinfilms of the invention have low leakage currents, show relatively littlegrowth of interfacial SiO₂, and thus have high specific capacitance withlow interface state density. The dielectric properties of the thin filmsproduced by the method disclosed herein are substantially improved overconventional silicon gate structures.

[0094] As used herein, the term “high temperature” refers to atemperature in excess of 800° C.

[0095] The invention in one embodiment relates to a CVD precursorcomposition for forming a thin film dielectric on a substrate, suchprecursor composition including a metalloamide source reagent compoundselected from the group consisting of:

M(NR¹R²)_(x);

[0096] and

[0097] wherein M is selected from the group consisting of: Zr, Hf, Y,La, Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹and R² is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6.

[0098] In a preferred embodiment, M is Zr or Hf, and R¹ and R² aremethyl and/or ethyl. In a more preferred embodiment, the metalloamidesource reagents useful for depositing dielectric thin films on asubstrate include but are not limited to, compounds of the formulaM(NMe₂)_(x), M(NEt₂)_(x.), M(NMeEt)_(x)

[0099] Examples of metalloamide compounds which may be usefully employedin the present invention include, without limitation, Zr(NMe₂)₄,Zr(NMeEt)₄, Zr(NEt₂)₄, Ta(NEt₂)₅, Ta(NMe₂)₅, Ta(NMeEt)₅, Zr(NiPr₂)₄,Zr(NMe₂)₂(NPr₂)₂, Zr(NC₆H₁₂)₄, Zr(NEt₂)₂(NPr₂)₂, Hf(NEt₂)₄, Hf(NMe₂)₄,Hf(NMeEt)₄, La(NMe₂)₃, La(NEt₂)₃, , La(NMeEt)₃, Al(NMe₂)₃, Al(NEt₂)₃,Y(NMe₂)₃, Y(NEt₂)₃, Y(NMeEt)₃, Ti(NMe₂)₄, Ti(NEt₂)₄, Ti(NMeEt)₄,Ta(NMe₂)₅, Ta(NEt₂)₅, wherein Me represents methyl, Et represents ethyl,Pr represents propyl, and iPr represents isopropyl. Preferredmetalloamide source reagent compounds useful in the present inventioninclude Zr(NMe₂)₄, Zr(NEt₂)₄, Hf(NEt₂)₄ and Hf(NMe₂)₄.

[0100] In a specific embodiment, the metalloamide source reagentcompound useful in the present invention may comprise an oligomer, i.e.Al₂(μ-NMe₂)₂(NMe₂)₄.

[0101] The metalloamide source reagents of the present invention areuseful for forming dielectric thin films including but not limited to:gate dielectrics, high dielectric constant metal oxides, andferroelectric metal oxides.

[0102] In one embodiment, the metalloamide source reagents are usefulfor forming gate dielectric thin films on a substrate, wherein the gatedielectric thin film may comprise a metal-oxide, a metal oxy-nitride, ametal silicate or a metal silicon-oxy-nitride. More preferably, themetalloamide source reagent is useful for forming a metal silicate gatedielectric thin film.

[0103] In a further embodiment, the present invention relates to a CVDprecursor composition for forming a thin film dielectric on a substrate,such precursor composition including at least one aminosilane sourcereagent compound selected from the group consisting of:

H_(x)SiA_(y)(NR¹R²)_(4−x−y);

[0104] and

[0105] wherein H is hydrogen; x is from 0 to 3; Si is silicon; A is ahalogen; Y is from 0 to 3; N is nitrogen; each of R¹ and R² is same ordifferent and is independently selected from the group consisting of H,aryl, perfluoroaryl, C₁-C₈ alkyl, and C₁-C₈ perfluoroalkyl; and n isfrom 1-6. Preferably, R¹ and R² are methyl and/or ethyl.

[0106] In a preferred embodiment, the aminosilane source reagentcompounds useful for depositing a dielectric thin film on a substrateinclude but are not limited to: Si(NMe₂)₃Cl, Si(NEt₂)₂Cl₂, Si(NMe₂)₄,and Si(NEt₂)₄.

[0107] The aminosilane source reagent compound may be used to depositsilicate or silicon oxy-nitride gate dielectric thin films on asubstrate or the aminosilane source reagent may be used in combinationwith the metalloamide source reagent composition, as describedhereinabove, to deposit a metal silicate or metal silicon-oxy-nitridegate dielectric thin film on a substrate.

[0108] The invention in a further embodiment relates to a CVD precursorcomposition for forming a thin film dielectric on a substrate, suchprecursor composition including a metalloamide vapor source reagentcompound selected from the group consisting of:

M(NR¹R²)_(x);

[0109] and

[0110] wherein M is selected from the group consisting of: Zr, Hf, Y,La, Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹and R² is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; x is the oxidation state on metal M; and n is from 1-6.

[0111] In a further embodiment the present invention relates to a CVDprecursor composition for forming a thin film dielectric on a substrate,such precursor composition including at least one aminosilane vaporsource reagent compound selected from the group consisting of:

H_(x)SiA_(y)(NR¹R²)_(4−x−y);

[0112] and

[0113] wherein H is hydrogen; x is from 0 to 3; Si is silicon; A is ahalogen; Y is from 0 to 3; N is nitrogen; each of R¹ and R² is same ordifferent and is independently selected from the group consisting of H,aryl, perfluoroaryl, C₁-C₈ alkyl, and C₁-C₈ perfluoroalkyl; and n isfrom 1-6.

[0114] In a preferred embodiment, R¹ and R² are methyl and/or ethyl. Ina more preferred embodiment, the aminosilane vapor source reagentcompounds usefully employed in the present invention include, withoutlimitation, Si(NMe₂)₃Cl, Si(NEt₂)₂Cl₂, Si(NMe₂)₄, and Si(NEt₂)₄.

[0115] In one embodiment of the present invention the metalloamide CVDprecursor composition is used to deposit a silicate gate dielectric thinfilm wherein the metalloamide precursor is suitably used in combinationwith a silicon precursor(s) source to yield the product metal silicatefilm. The silicon precursor may advantageously comprise an aminosilanesource reagent compound as described herein or may alternativelycomprise an alternative silicon source reagent compound as known tothose skilled in the art, to deposit silicate thin films, (e.g.. silane,trimethylsilane, tetramethylsilane and tetraethylorthosilicate).

[0116] In a further embodiment of the present invention the metalloamideCVD precursor composition is bi-functional in that it may be used todeposit a gate dielectric thin film and a gate conductor, wherein thegate dielectric thin film is first deposited on a substrate using CVDconditions as described herein followed by deposition of a gateconductor on the gate dielectric substrate. The bi-functional nature ofthe metalloamide source reagent compound is advantageous in that itlimits the number of process steps necessary to produce two componentsof a device structure. As an example, in a first step, a (Hf, Si)₄ gatedielectric thin film is CVD deposited on a substrate from Hf(NMe₂)₄,Si(NMe₂)₄ and N₂O process gas. In a second step, a HfN gate conductor isdeposited on the (Hf, Si)O₄ gate dielectric thin film of step one, fromHf(NMe₂)₄ and NH₃ process gas. This is especially useful for NMOS, wherethe fermi level of the gate conductor should be well matched to that inthe channel.

[0117] By utilizing a precursor composition including at least onemetalloamide source reagent compound and at least one aminosilane sourcereagent compound, to produce a metal silicate dielectric thin film on asubstrate, with the metalloamide source reagent compound containing atleast part of the metal to be incorporated in the product dielectricmetal silicate film, and the aminosilane source reagent compoundcontaining at least part of the silicon to be incorporated in theproduct dielectric metal silicate film, it is possible by selection ofthe proportions of such respective compounds to correspondingly vary thestoichiometric composition (metal/silicon ratio) of the metal silicatedielectric film, to obtain a desired character of structural andperformance properties in the product film. For example, an aminosilanesource reagent compound, containing no metal, may be used in combinationwith a metalloamide source reagent compound, containing no silicon, tocontrol film ratios, (i.e., Zr/Si or Hf/Si).

[0118] In one embodiment, the present invention relates to a CVDprecursor composition for forming a silicate thin film dielectric on asubstrate, such precursor including a vapor source mixture comprising atleast one metalloamide vapor source reagent compound as describedhereinabove and at least one aminosilane vapor source reagent compoundas described hereinabove, wherein the relative proportions of theaminosilane vapor source reagent and the metalloamide vapor sourcereagent relative to one another are employed to controllably establishthe desired M_(x)/Si_(1−x) ratio in the deposited silicate thin films,wherein M_(x)/Si1 _(1−x) is from about 0.01 to 10. The exact compositionwill be a trade off between high Si films, which prevent crystallizationduring subsequent high temperature processing, and high M films, whichhave higher dielectric constant (lower EOT).

[0119] In a further embodiment the present invention relates to a CVDprecursor solution composition for forming a thin film dielectric on asubstrate, such precursor composition including at least onemetalloamide compound as described hereinabove and a solvent medium inwhich the metalloamide compound is soluble or suspendable, wherein themetalloamide compound and the solvent medium are combined to produce aprecursor solution mixture for depositing a dielectric thin film on asubstrate.

[0120] In a further embodiment the present invention relates to a CVDprecursor solution composition for forming a thin film dielectric on asubstrate, such source reagent composition including at least oneaminosilane compound as described hereinabove and a solvent medium inwhich at least one aminosilane compound is soluble or suspendable,wherein the aminosilane precursor compound and the solvent medium arecombined to produce a precursor solution mixture for depositing asilicon containing dielectric thin film on a substrate.

[0121] In a further embodiment, the present invention relates to a CVDmulti-component, single source precursor composition useful for forminga thin film dielectric on a substrate, such source composition includingat least one metalloamide compound as described hereinabove, at leastone aminosilane compound as described hereinabove and a solvent mediumin which the metalloamide compound and the aminosilane compound aresoluble or suspendable, wherein the metalloamide source reagentcompound, the aminosilane compound, and the solvent medium are combinedto produce a chemically compatible, single source solution mixture fordepositing a silicon containing dielectric thin film on a substrate.

[0122] Providing a precursor composition in liquid (i.e., neat solutionor suspension) form facilitates rapid volatilization (i.e., flashvaporization) of the source reagent composition and transport of theresultant precursor vapor to a deposition locus such as a CVD reactionchamber. The metalloamide and aminosilane compounds of the presentinvention are chosen to provide a degenerate sweep of ligands, toeliminate ligand exchange and to provide a robust precursor delivery,gas-phase transport and CVD process.

[0123] The precursor compositions of the present invention may compriseany suitable solvent medium that is compatible with the metalloamideand/or aminosilane compounds contained therein. The solvent medium insuch respect may comprise a single component solvent, or alternatively asolvent mixture or solution. Illustrative solvent media that may bevariously usefully employed include ethers, glymes, tetraglymes, amines,polyamines, aliphatic hydrocarbon solvents, aromatic hydrocarbonsolvents, cyclic ethers, and compatible combinations of two or more ofthe foregoing. A particularly preferred solvent species useful in thepractice of the present invention is octane.

[0124] The source reagent compounds of the invention are stable, even inorganic solutions, while at the same time they are volatilizable at lowtemperatures that are consistent with efficient chemical vapordeposition processing. The source reagent compounds of the presentinvention also possess the following advantageous features: gooddeposition rates; good thermal stability; higher elemental purity;formation of essentially carbon-free films (in contrast to the reportedliterature, i.e. Jones, et al., “MOCVD of Zirconia Thin Films by DirectLiquid Injection Using a New Class of Zirconium Precursor”, Chem. Vap.Dep., Vol. 4, 1998, PP. 46-49.); limited SiO₂ interlayer formation;ready decomposition at CVD process temperatures; and good solubility ina wide variety of organic solvents and solvent media.

[0125] Here and throughout this disclosure, where the invention providesthat at least one aminosilane compound and one metalloamide compound arepresent in a composition or method, the composition or method maycontain or involve additional, (i.e., third and fourth) metalloamideand/or aminosilane compounds.

[0126] The metalloamide and aminosilane source reagent compounds of theinvention and methods of making are well known in the art and may beobtained from commercial sources or readily prepared by publishedsynthetic routes. See, D. C. Bradley and I. M. Thomas, “MetalorganicCompounds Containing Metal-Nitrogen Bonds: Part I. Some DialkylaminoDerivatives of Titanium and Zirconium”, J. Chem. Soc., 1960, 3857) (D.C. Bradley and I. M. Thomas, “Metalorganic Compounds ContainingMetal-Nitrogen Bonds: Part III. Dialkylamino Compounds of Tantalum”,Canadian J. Chem., 40, 1355 (1962). Many of the metalloamide andaminosilane source reagent compounds of the present invention areavailable commercially through ATMI, Inc., Inorgtech, Gelest, Inc.,Aldrich Chemical Company and Strem Chemical Company.

[0127] In a further embodiment the present invention relates to a methodfor forming a dielectric thin film on a substrate by chemical vapordeposition.

[0128] Such method includes the steps of:

[0129] vaporizing a precursor composition comprising at least onemetalloamide source reagent compound selected from the group consistingof:

M(NR¹R²)_(x);

[0130] and

[0131] wherein M is selected from the group consisting of: Zr, Hf, Y,La, Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹and R² is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C8 perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6;

[0132] , as described hereinabove, to form a source reagent precursorvapor;

[0133] transporting such source reagent precursor vapor into a chemicalvapor deposition zone containing a substrate, optionally using a carriergas to effect such transport;

[0134] contacting the source reagent precursor vapor with a substrate insuch chemical vapor deposition zone in the presence of an oxidizer andat elevated temperature to deposit a corresponding M containingdielectric thin film.

[0135] In a further embodiment the present invention relates to a methodfor forming a dielectric silicate thin film on a substrate by chemicalvapor deposition.

[0136] Such method includes the steps of:

[0137] vaporizing a precursor composition comprising at least oneaminosilane compound selected from the group consisting of:

H_(x)SiA_(y)(NR¹R²)_(4−x−y);

[0138] and

[0139] as described hereinabove, to form a source reagent precursorvapor;

[0140] transporting such source reagent precursor vapor into a chemicalvapor deposition zone containing a substrate, optionally using a carriergas to effect such transport;

[0141] contacting the source reagent precursor vapor with a substrate insuch chemical vapor deposition zone in the presence of an oxidizer andat elevated temperature to deposit a corresponding Si containingdielectric thin film.

[0142] The metalloamide and aminosilane compounds of the presentinvention may be used independently or in combination to form thedesired dielectric thin film. When used in combination, the metalloamideand aminosilane compound may be vaporized and deposited simultaneouslyor sequentially to obtain a dielectric thin film having the desiredproperty.

[0143] The particular CVD method used to deposit the dielectric thinfilms of the present invention may be one of many known to those skilledin the art. Particularly preferred CVD methods for delivery anddeposition of the metalloamide and aminosilane source reagent compoundsof the present invention include liquid delivery chemical vapordeposition (LDCVD) and atomic layer chemical vapor deposition (ALCVD).

[0144] In an atomic layer chemical vapor deposition embodiment, ametalloamide precursor vapor is introduced into a chemical vapordeposition chamber comprising a substrate, in a sequential or “pulsed”deposition mode, during which time, extremely co-reactive gases may beemployed, such as ozone, water vapor or reactive alcohols, that mightnormally be expected to produce deleterious deposition effects on theCVD process (i.e., gas phase particle formation).

[0145] In a further embodiment, the atomic layer chemical vapordeposition method of the present invention, may further comprise anaminosilane precursor vapor that may be simultaneously co-pulsed andco-deposited with the metalloamide precursor vapor, on a substrate.Alternatively, the aminosilane precursor vapor may be deposited on asubstrate in a sequential pulsing method, wherein the aminosilanecompound alternates pulses with the metalloamide compound. Thedielectric thin films are built up by introducing short bursts of gasesin cycles.

[0146] In a further embodiment, a co-reactant may be used in a pulsed oratomic layer chemical vapor deposition method, wherein the metalloamideprecursor and/or aminosilane precursor vapor is separated from theco-reactant by time in the pulse track. The co-reactant may be utilizedto facilitate the decomposition of the precursor on a substrate, withina desired temperature regime and to produce carbon-free dielectricthin-films. As an example, the use of water vapor may be utilized toinduce a lower decomposition temperature of the aminosilane precursorvapor, which in some instances has been found to be stable in oxidizingenvironments such as N₂O.

[0147] The specific nature of the pulse track and number of cycles maybe varied. In a typical ALCVD process, a cycle lasts from 1-5 seconds.The following non-limiting examples demonstrate various pulse tracksdefining precursor(s) and co-reactant(s) that may be successfully usedto deposit the dielectric thin films of the present invention:

[0148] example track 1-(metalloamide/purge (inert)/co-reactant+N₂O/purge(inert))n cycles;

[0149] example track 2-(metalloamide+aminosilane/purge (inert)/N₂O/purge(inert))n cycles;

[0150] example track 3-(metalloamide+co-reactant N₂O/co-reactant watervapor/purge (inert))n cycles;

[0151] example track 4- (metalloamide+co-reactantN₂O/aminosilane/co-reactant water vapor/purge (inert))n cycles.

[0152] wherein n is an integer number, typically ranging from 10 to 100,and different co-reactants have different oxidizing potentials.

[0153] In liquid delivery CVD, the source liquid may comprise the sourcereagent compound(s) if the compound or complex is in the liquid phase atambient temperature (e.g.., room temperature, 25° C.) or other supplytemperature from which the source reagent is rapidly heated andvaporized to form precursor vapor for the CVD process. Alternatively, ifthe source reagent compound or complex is a solid at ambient or thesupply temperature, such compound or complex can be dissolved orsuspended in a compatible solvent medium therefore to provide a liquidphase composition that can be submitted to the rapid heating andvaporization to form precursor vapor for the CVD process. The precursorvapor resulting from the vaporization then is transported, optionally incombination with a carrier gas (e.g.., He, Ar, H₂, O₂, etc.), to thechemical vapor deposition reactor where the vapor is contacted with asubstrate at elevated temperature to deposit material from the vaporphase onto the substrate or semiconductor device precursor structurepositioned in the CVD reactor.

[0154] The precursor liquid may be vaporized in any suitable manner andwith any suitable vaporization means to form corresponding precursorvapor for contacting with the elevated temperature substrate on whichthe dielectric film is to be formed. The vaporization may for example becarried out with a liquid delivery vaporizer unit of a type ascommercially available from Advanced Technology Materials, Inc.(Danbury, Conn.) under the trademark SPARTA and VAPORSOURCE II, in whichprecursor liquid is discharged onto a heated vaporization element, suchas a porous sintered metal surface, and flash vaporized. The vaporizermay be arranged to receive a carrier gas such as argon, helium, etc. andan oxygen-containing gas may be introduced as necessary to form thedielectric thin film. The precursor vapor thus is flowed to the chemicalvapor deposition chamber and contacted with the substrate on which thedielectric film is to be deposited. The substrate is maintained at asuitable elevated temperature during the deposition operation by heatingmeans such as a radiant heating assembly, a susceptor containing aresistance heating element, microwave heat generator, etc. Appropriateprocess conditions of temperature, pressure, flow rates andconcentration (partial pressures) of metal and silicon components aremaintained for sufficient time to form the dielectric film at thedesired film thickness, (i.e., in a range of from about 2 nanometers toabout 1000 micrometers), and with appropriate dielectric filmcharacteristics.

[0155] The step of vaporizing the source reagent compounds of thepresent invention is preferably carried out at a vaporizationtemperature in the range of from about 50° C. to about 300° C. Withinthis narrow range of vaporization temperature, the metalloamide andaminosilane source reagent compounds are effectively vaporized with aminimum extent of premature decomposition.

[0156] In the optional use of a carrier gas in the practice of thepresent invention, for transporting the vaporized source reagentcomposition into the chemical vapor deposition zone, suitable carriergas species include gases that do not adversely affect the dielectricfilm being formed on the substrate. Preferred gases include argon,helium, krypton or other inert gas, with argon gas generally being mostpreferred. In one illustrative embodiment, argon gas may be introducedfor mixing with the vaporized source reagent composition at a flow rateof about 100 standard cubic centimeters per minute (sccm).

[0157] Oxidizing gases useful for the broad practice of the presentinvention include, but are not limited to, O₂, N₂O, NO, H₂O and O₃, Morepreferably, the oxidizer used comprises N₂O.

[0158] The deposition of the dielectric thin films of the presentinvention are preferably carried out under an elevated depositiontemperature in a range of from about 250° C. to about 750° C.

[0159] By way of example, Hf(NMe₂)₄ and Si(Me)₄ may be mixed in a gasstream, (i.e., in a carrier gas), and mixed in the gas stream to the CVDreactor to produce the appropriate stoichiometry in a deposited HfSiO₄thin-film. Other metalloamides of the invention and silanes may besimilarly employed with equivalent success, provided that the respectiveligands do not produce undesirable non-degenerate ligand exchangesforming (undesired) new precursor species. It therefore is preferred touse the same ligand species, (i.e., methyl, ethyl, phenyl, etc.) foreach of the metalloamide and silicon precursors used in combination withone another.

[0160] By way of further example, Hf(NMe₂)₄ and Si(NMe₂)₄ may be mixedin a gas stream, (i.e., in a carrier gas), and mixed in the gas streamto the CVD reactor to produce the appropriate stoichiometry in adeposited Hf_(x)Si_(2−x)O₄ thin-film, wherein x is from 0 to 1 . Othermetalloamides of the invention and aminosilanes may be similarlyemployed with equivalent success, provided that the respective ligandsdo not produce undesirable non-degenerate ligand exchanges forming(undesired) new precursor species. It therefore is preferred to use thesame ligand species, (i.e., methyl, ethyl, phenyl, etc.) for each of themetalloamide and aminosilane precursors used in combination with oneanother.

[0161] By way of further example, a representative liquid deliverychemical vapor deposition approach is illustrated by the use ofmetalloamide source reagent compound, Zr(NMe₂)₄ and aminosilane sourcereagent compound Si(NMe₂)₄. The source reagent compounds are introducedinto a chemical vapor deposition chamber using liquid delivery andoxidized in-situ to deposit on a substrate, the desired Zr silicate thinfilm composition based upon electrical performance and filmstoichiometry. La(NMe₂)₃ may be added to the mixture to produce a Zr Ladoped silicate dielectric film under similar processing conditions.

[0162] By way of further example, a representative liquid deliverychemical vapor deposition approach is illustrated by the use ofmetalloamide source reagent compound, Y(NMe₂)₃ and aminosilane sourcereagent compound Si(NEt₂)₄. The source reagent compounds are introducedinto a chemical vapor deposition chamber using liquid delivery andoxidized in-situ to deposit on a substrate, the desired Y silicate thinfilm composition based upon electrical performance and filmstoichiometry.

[0163] By way of further example, a representative liquid deliverychemical vapor deposition approach is illustrated by the use ofmetalloamide source reagent compounds Hf(NMe₂)₄ and La(NMe₂)₃ andaminosilane source reagent compound Si(NEt₂)₄. The source reagentcompounds are introduced into a chemical vapor deposition chamber usingliquid delivery and oxidized in-situ to deposit on a substrate, thedesired HfLa silicate thin film composition based upon electricalperformance and film stoichiometry. Zr(NMe₂)₄ may be added to themixture to produce Zr doped silicate films under similar processingconditions.

[0164] As evidenced hereinabove, it is possible to use respectivemetalloamides and aminosilane compounds, (i.e., alkyl, and phenylcompounds), regardless of ligand identity and ligand exchangemechanisms, by the use of techniques such as atomic layer or pulsed CVDmethod, in which the incompatible precursors are separated bothtemporally and in the introduction lines to limit particle formation andundesired ligand exchange reactions.

[0165] In a further embodiment, the present invention relates to adielectric thin film, having a dielectric constant value in a rangebetween about 4 to about 60 as measured at a frequency of 1 mega-Hertz,produced by a method comprising the steps of:

[0166] vaporizing a precursor composition comprising at least onemetalloamide compound selected from the group consisting of:

M(NR¹R²)_(x);

[0167] and

[0168] as described hereinabove, to form a source reagent precursorvapor;

[0169] transporting such source reagent precursor vapor into a chemicalvapor deposition zone containing a substrate, optionally using a carriergas to effect such transport;

[0170] contacting the source reagent precursor vapor with a substrate insuch chemical vapor deposition zone in the presence of an oxidizer andat elevated temperature to deposit a corresponding M containingdielectric thin film.

[0171] In a further embodiment the present invention relates to asilicon containing dielectric thin film, having a dielectric constant ina range between about 4 to about 60 as measured at a frequency of 1mega-Hertz, by a method comprising the steps:

[0172] vaporizing a source reagent precursor composition comprising atleast one aminosilane compound selected from the group consisting of:

H_(x)SiA_(y)(NR¹R²)_(4−x−y);

[0173] and

[0174] as described hereinabove, to form a source reagent precursorvapor;

[0175] transporting such source reagent precursor vapor into a chemicalvapor deposition zone containing a substrate, optionally using a carriergas to effect such transport;

[0176] contacting the source reagent precursor vapor with a substrate insuch chemical vapor deposition zone in the presence of an oxidizer andat elevated temperature to deposit a corresponding silicate dielectricthin film.

[0177] The dielectric metal silicate thin films produced from themetalloamide materials of the present invention are pure metal silicatethin films comprising little or no carbon or halogen impurity. In apreferred embodiment the dielectric silicate thin films contain lessthan 1 atomic percent carbon and more preferably the thin films containless than 1 ppm carbon and no detectable halogen.

[0178] The dielectric silicate films produced in the broad practice ofthe invention include stoichiometric metal silicate films, as well asoff-stoichiometric (metal-deficient) films. Where the precursorcomposition includes different source reagents providing respectivelydifferential metal and/or silicon content, then the respective sourcereagents can be supplied in varied compositions to achieve desiredstoichiometric characteristics in the corresponding product metalsilicate films. In this manner, the electrical properties, includingdielectric constant and leakage, can be controlled and closely tailoredto a desired end use.

[0179] The dielectric thin films produced by a method of the presentinvention are useful as, but not limited to: gate dielectric thin films,more particularly metal silicate gate dielectric thin films and metaloxy-nitride gate dielectric thin films; metal oxide high dielectric thinfilms; and ferroelectric thin films.

[0180] The presence of nitrogen, in at least a partial thickness of thegate dielectric helps to prevent the diffusion of boron, such as from aboron-doped polysilcon gate electrode, to the channel region.

[0181] Exemplary dielectric thin films formed by the method of thepresent invention include but are not limited to: ZrSiO₄; HfSiO₄;Ta_(1−x)Al_(x)O_(y), where x is 0.03-0.7 and y is 1.5-205;Ta_(1−x)Si_(x)O_(y), where x is 0.05-0.15 and y is 1.5-3;Ta_(1−x−z)Al_(x)Si_(z)O_(y), where 0.7>x+z>0.05, z<0.15 and y is 1.5-3;HfO₂; ZrO₂; Ta₂O₅; Zr_(x)Si_(2−x)O₄ where x is 0.2-1.6;Hf_(x)Si_(2−x)O₄, where x is 0.2-1.6; Hf_(x)La_(y)Si_(2−x)O_(4+1.5y),where x is 0.2-1.6 and y is 0-1; Zr_(x)La_(y)Si_(2−x)O_(4+1.5y), where xis 0.2-1.6 and y is 0-1; Hf_(x)Al_(y)Si_(2−x)O_(4+1.5y), where x is0.2-1.6 and y is 0-0.2; Zr_(x)Al_(y)Si_(2−x)O_(4+1.5y), where x is0.2-1.6 and y is 0.02.

[0182] The features, aspects and advantages of the present invention arefurther shown with reference to the following non-limiting examplesrelating to the invention.

EXAMPLES

[0183] Process and Chemistry for Deposition of Hafnia Films fromAlkylamido Precursors

[0184] HfO₂ is a component of many of the proposed alternative high kgate dielectrics. One of the issues in growing a gate dielectric by aCVD process is minimizing the growth of interfacial SiO₂. There is someevidence that interfacial SiO₂ will grow even if the only oxygen presentin the process is in an oxygen-containing precursor, such as an alkoxideor a mixed alkoxide-β-diketonate. In order to avoid this possibility,the viability of alkyl-amido Hf, specifically, Hf(NMe₂)₄ and Hf(NEt₂)₄hereafter referred to as TDMAHf and TDEAHf, respectively, has beenstudied.

[0185] Carbon-free HfO₂ can be grown at high deposition rates from theseprecursors at temperatures down to 400° C. in an ambient of N₂O. It isquite unexpected that N₂O is effective at oxidizing the precursor atsuch low temperatures and there is no sign of the process getting worseat lower temperatures either with increase carbon or lower depositionrate.

[0186] The results described herein are extendable to the growth of awide range of oxide films at low temperatures. Notably, Ta₂O₅ and dopedTa₂O₅ might also grow as clean amorphous films at low temperatures fromalkylamido precursors in N₂O.

[0187] Experiment

[0188] Hafnia films were grown with the precursors listed in Table I.Precursor solutions were prepared at 0.1M Hf in octane. Substrate of(100) Si was prepared with an SC1 treatment followed by dilute HF toremove any SiO₂ on the surface. The generic process conditions for theexperiments are shown in Table II. Initially, films were grown at 550°C. under three different reactive gas conditions: Ar, N₂O and O₂.Results described below indicated that N₂O was the preferred ambient. Apressure-temperature matrix was performed for each precursor using theN₂O ambient as shown in FIGS. 2A and 2B. FIGS. 2A and 2B show theprocess space experiments for TDEAHf and TDMAHf precursors. At the end,a film targeting 50 Å was grown from each precursor to be used for TEMexamination of the interface with Si. TABLE I Precursors used for filmdeposition. Tetrakis(diethyl-amino)hafnium Hf(N(C₂H₅))₄ TDEAHfTetrakis(dimethyl-amino)hafnium Hf(N(CH₃))₄ TDMAHf

[0189] TABLE II Generic process conditions for zirconia and hafnia filmsPrecursor solution 0.10 M in octane Precursor solution delivery rate0.10 ml/min Vaporization Temperature 150° C. Run time  10-30 minutesCarrier gas 100 sccm Ar Heating and Cooling process gas 500 sccm Ar Runtime process gas 400 sccm N₂O or O₂ Pressure 0.8, 2.2, or 8.0 TorrTemperature 400-600° C. wafer surface

[0190] Film thickness was measured using single-wavelength ellipsometryat 70° incidence angle, and XRF. For HfO₂, the XRF was calibrated byassuming the X-ray efficiencies were equivalent to TaO_(2.5), for whichwe have standards that have been measured by RBS.

[0191] Results

[0192] The growth rate of hafnia was measured by XRF for films grown indifferent oxidizing ambients at 8 Torr and 550° C. as shown in FIG. 3.The compositions of these films were measured by XPS. The films grown inthe inert Ar environment had a high growth rate, but this growth wasaccompanied by considerable carbon and some nitrogen incorporation.Films grown in N₂O were surprisingly carbon-free, but with a low growthrate. No film growth was detected for the run performed in O₂. Withthese results, further examination of pressure and temperature wereperformed in a N₂O ambient.

[0193] The growth rate as measured by XRF varied over process space forthe two precursors as shown in FIGS. 4A and 4B. For both precursors, thegrowth rate is low at higher temperatures and pressures. At the 0.8Torr, growth rate is largely independent of temperature, and at 400° C.the growth rate is largely independent of pressure. The growth rate ofTDEAHf is slightly lower than TDMAHf, but both have rates that aresufficient for manufacturable deposition.

[0194] The RMS roughness of the films was measured by AFM over a 1×1 μmareas and the results plotted as a function of film thickness as shownin FIG. 5. Films generally roughen somewhat as they become thicker, sothat it is important to compare their morphology to others of the samethickness. For both precursors, films grown at 400° C. are smoother thanthose grown at higher temperatures. The growth time was shorter for theTDMAHf films, so they were much thinner and also smoother. A film wasgrown for each precursor to a thickness of about 50 Å. In both cases,the RMS roughness was about 6 Å.

[0195] Film thickness and index of refraction were measured byellipsometry for all films. Those grown from TDEAHf were thick and theresulting roughness prevented reliable ellipsometry measurements. Theindex of refraction of the films grown from TDMAHf is shown as afunction of process condition in FIG. 6. The films grown at lowertemperature exhibited higher refractive index, which probably indicateseither a more dense film or a film with less SiO₂ incorporated from thesubstrate.

[0196] The XPS analysis of composition for the TDEAHf and for the TDMAHfdemonstrated that all process conditions had negligible carbonincorporation (<1%). For the TDEAHf, there seems to be an increase inoxygen to Hf ratio at higher pressures, 8 Torr, and intermediatetemperatures, 500° C. For the TDMAHf, there was less change instoichiometry with condition, with highest oxygen concentrations at 400°C. From past experience, the highest oxygen content films have had thelowest leakage for a particular capacitance.

[0197] TEM was used to examine the interface of a nominal 50 Å filmgrown from each of the precursors at 400° C. Film G161 was grown at 400°C., 8 Torr from TDMAHf with a growth time of 43 seconds; Film G163 wasgrown at 400° C., 0.8 Torr from TDEAHf with a growth time of 60 seconds.TEM showed the interfaces of both films with underlying Si to be cleanof any interfacial silicon oxide. In addition, it is clearly shown thatthe films are crystalline. It is expected that mixing Si oxide with theHf oxide in the growth process would yield an amorphous film.

[0198] Process and Chemistry for Deposition of Hafnium Silicate Filmsfrom Alkylamido Precursors

[0199] One of the issues in growing a gate dielectric by a CVD processis minimizing the growth of interfacial SiO₂. There is some evidencethat interfacial SiO₂ will grow even if the only oxygen present in theprocess is in an oxygen-containing precursor, such as an alcoxide or amixed alcoxide-β-diketonate. The experiment discussed hereinabovedemonstrated the viability of two hafnia precursors specifically,Hf(NMe₂)₄ and Hf(Net₂)₄ hereafter referred to as TDMAHf and TDEAHf,respectively. This experiment examines the viability of thecorresponding silicon precursors: Si(NMe₂)₃Cl and Si(NEt₂)₂Cl₂. Thesilica precursors are examined using the same process conditions.

[0200] The growth rates of both precursors are too low for a viablesilica process in N₂O over the temperature and pressure range examined(0.8 to 8 Torr, 400-600° C.). This is not surprising based on the growthrates of precursors such as bis(tertiarybutylamino) silane H₂Si(N-tBu)₂(i.e., U.S. Pat. No. 5,976,991) at temperatures below 600° C. What isunexpected is that although growth rates for SiO₂ from Si(NMe₂)₃Cl andSi(NEt₂)₂Cl₂ is slow in a N₂O atmosphere, the presence of Hf enhancesthe decomposition of Si(NEt₂)₂Cl₂ to create a mixed Hf-Si-O film atmanufacturable growth rates. Additionally, oxygen ambients attemperatures below 500° C. might be viable with the hafnium precursors.

[0201] Experimental

[0202] Silica films were grown with the silicon precursors listed inTable III, Si(NMe₂)₃Cl and Si(NEt₂)₂Cl₂. Precursor solutions wereprepared at 0.1M Si in octane. Substrates of (100) Si were prepared withan SC1 treatment followed by dilute HF to remove any native SiO₂. Thegeneric process conditions for the experiments are shown in Table IV.Results from the growth of hafnia films encouraged us to center theseinitial experiments on growth in an N₂O atmosphere although growth in O₂or other oxidizer could be used at temperatures at or below 500° C. Alimited pressure-temperature matrix was performed for each Si precursorusing the N₂O ambient as shown in FIG. 7A and 7B. TABLE III Precursorsused for film deposition. (Bis(diethyl-amino)dichlorosilane)Si(N(C₂H₅)₂)₂Cl₂ (Tris(dimethyl-amino)chlorosilane) Si(N(CH₃)₂)₃ClTetrakis(diethyl-amino)hafnium Hf(N(C₂H₅)₂)₄ TDEAHfTetrakis(dimethyl-amino)hafnium Hf(N(CH₃)₂)₄ TDMAHf

[0203] TABLE IV Generic process conditions Precursor solution 0.10 M inoctane Precursor solution delivery rate 0.10 ml/mm VaporizationTemperature 150° C. Run time  10 minutes Carrier gas 100 sccm Ar Heatingand Cooling process gas 500 sccm Ar Run time process gas 400 sccm N₂OPressure 0.8, 2.2, or 8.0 Torr Temperature 400-650° C. wafer surface

[0204] From NMR studies of precursor compatibility, it was shown thatSi(NEt₂)₂Cl₂ is compatible with TDEAHf in solution, with any ligandexchange being degenerate. Si(NMe₂)₃Cl is compatible with both TDEAHfand TDMAHf. A solution of 0.05M TDEAHf:0.05M Si(NEt₂)₂Cl₂ was producedby mixing the two 0.1M solutions. This mixture was used to grow filmsover the entire matrix of process conditions.

[0205] Film thickness was measured using single-wavelength ellipsometryat 70° incidence angle, and XRF. For SiO₂ deposition, all films wereless than 30 Å thick, so an index of refraction could not be measuredaccurately. Film thickness was assigned based on an assumed index ofrefraction, n=1.46, typical of high quality thermal oxide. For HfO₂, theXRF was calibrated by assuming the X-ray efficiencies were equivalent toTaO_(2.5), for which standards that been measured by RBS. The Hf:Sicomposition was estimated by assuming that both are filly oxidized andfully dense. The ellipsometric thickness not accounted for by HfO₂ wasassigned to SiO₂, and composition was calculated from these twothicknesses.

[0206] Results

[0207] Growth rates of SiO₂ were less than 3 Å/min under all conditionsas shown in FIG. 8 and FIG. 9. There is some indication that theSi(NEt₂)₂Cl₂ may form silica films a little bit more readily, however,none of the growth rates are sufficient for the two precursors under theinstant conditions.

[0208] The growth of SiO₂ with only the TDEAHf, as measured by thesubtraction of ellipsometric thickness from XRF thickness (shown in FIG.10) was greater than that from the Si(NEt₂)₂Cl₂ precursor alone (FIG. 8)Films grown from the precursor mixture (TDEAHf+Si(NEt₂)₂Cl₂) showedstill higher SiO₂ growth rates as shown in FIG. 11. This increasedgrowth rate compared to FIG. 8 is unexpected and should be quite usefulfor the growth of hafnium silicate films of uniform Hf:Si compositionthrough the thickness of the film.

[0209] The films have a mixed Si:Hf composition on the film surface. Theconstant SiO₂ growth rate over the range of 500-600° C. at 2.2 Torrbeing the same as 0.8 Torr at 600° C. is taken as evidence of masstransport limited deposition over the range of the process. The additionof water vapor or O₂, should further decrease the temperature windowwherein both Hf and Si alkylamido precursors transport and decomposereliably.

What is claimed is:
 1. A CVD precursor composition for forming a thinfilm dielectric on a substrate, such precursor composition including atleast one metalloamide source reagent compound selected from the groupconsisting of: M(NR¹R²)_(x); and

wherein M is selected from the group consisting of: Zr, Hf, Y, La,Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹ and R²is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6.2. The CVD precursor according to claim 1, wherein n is
 5. 3. The CVDprecursor according to claim 1, wherein n is
 6. 4. The CVD precursoraccording to claim 1, wherein R¹ is methyl and R² is ethyl.
 5. The CVDprecursor composition according to claim 1, wherein the metalloamidesource reagent compound is selected from the group consisting of:Zr(NMe₂)₄, Zr(NMeEt)₄, Zr(NEt₂)₄, Ta(NEt₂)₅, Ta(Ne₂)₅, Ta(NMeEt)₅,Zr(NiPr₂)₄, Zr(NMe₂)₂(NPr₂)₂, Zr(NC₆H₁₂)₄, Zr(NEt₂)₂(NPr₂)₂, Hf(NEt₂)₄,Hf(NMe₂)₄, Hf(NMeEt)₄, La(NMe₂)₃, La(NEt₂)₃, La(NMeEt)₃, Al(NMe₂)₃,Al(NEt₂)₃, Y(NMe₂)₃, Y(NEt₂)₃, Y(NMeEt)₃, Ti(NMe₂)₄, Ti(NEt₂)₄,Ti(NMeEt)₄, Ta(NMe₂)₅, Ta(NEt₂)₅.
 6. The CVD precursor compositionaccording to claim 1, wherein the metalloamide source reagent compoundis selected from the group consisting of Zr(NMe₂)₄, Zr(NEt₂)₄,Zr(NMeEt)₄, Hf(NMe₂)₄, Hf(NEt₂)₄ and Hf(NMeEt)₄.
 7. The CVD precursorcomposition according to claim 1, wherein the precursor compositionfurther comprises a solvent medium selected from the group consistingof: ethers, glymes, tetraglymes, amines, polyamines, alcohols, glycols,aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, cyclicethers and combinations of two or more of the foregoing.
 8. The CVDprecursor composition according to claim 7, wherein the precursorcomposition further comprises a solvent medium selected from the groupconsisting of: ethers, glymes, tetraglymes, amines, polyamines,alcohols, glycols, aliphatic hydrocarbon solvents, aromatic hydrocarbonsolvents, cyclic ethers and combinations of two or more of theforegoing.
 9. The CVD precursor composition according to claim 7,wherein the solvent is octane.
 10. The CVD precursor compositionaccording to claim 1, wherein the metalloamide source reagent compoundis injected by liquid delivery into a chemical vapor deposition chamber.11. The CVD precursor composition according to claim 1, wherein themetalloamide source reagent compounds is delivered by bubbler into achemical vapor deposition chamber.
 12. The method of claim 1 wherein theprecursor composition further comprises an aminosilane source reagentcompound selected from the group consisting of:H_(x)SiA_(y)(NR¹R²)_(4−x−y); and

wherein H is hydrogen; x is from 0 to 3; Si is silicon; A is a halogen;Y is from 0 to 3; N is nitrogen; each of R¹ and R² is same or differentand is independently selected from the group consisting of H, aryl,perfluoroaryl, C₁-C₈ alkyl, and C₁-C₈perfluoroalkyl; and n is from 1-6.13. The CVD precursor composition according to claim 12, wherein theaminosilane source reagent is selected from the group consisting of:Si(NMe₂)₃Cl, Si(NEt₂)₂Cl₂, Si(NMe₂)₄, and Si(NEt₂)₄.
 14. The CVDprecursor composition according to claim 12, wherein the metalloamidesource reagent compound and the aminosilane source reagent compound areinjected by liquid delivery into a chemical vapor deposition chamber.15. The CVD precursor composition according to claim 12, wherein themetalloamide source reagent compound and the aminosilane source reagentcompound are delivered by bubbler into a chemical vapor depositionchamber.
 16. The CVD precursor composition according to claim 1, whereinthe precursor composition comprises multiple metalloamide source reagentcompounds.
 17. The CVD precursor composition according to claim 12,wherein the precursor composition further comprises a solvent mediumselected from the group consisting of: ethers, glymes, tetraglymes,amines, polyamines, alcohols, glycols, aliphatic hydrocarbon solvents,aromatic hydrocarbon solvents, cyclic ethers and combinations of two ormore of the foregoing.
 18. The CVD precursor composition according toclaim 12, wherein the metalloamide source reagent compounds areco-injected by liquid delivery into a chemical vapor deposition chamber.19. The CVD precursor composition according to claim 1, wherein themetalloamide source reagent compound is dissolved or suspended in asolvent, wherein the solvent is selected from the group consisting of:ethers, glymes, tetraglymes, amines, polyamines, alcohols, glycols,aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, cyclicethers and combinations of two or more of the foregoing.
 20. A CVDprecursor composition for forming a thin film dielectric on a substrate,such precursor composition including at least one aminosilane sourcereagent compound selected from the group consisting of:H_(x)SiA_(y)(NR¹R²)_(4−x−y); and

wherein H is hydrogen; x is from 0 to 3; Si is silicon; A is a halogen;Y is from 0 to 3; N is nitrogen; each of R¹ and R² is same or differentand is independently selected from the group consisting of H, aryl,perfluoroaryl, C₁-C₈ alkyl, and C₁-C₈ perfluoroalkyl; and n is from 1-6.21. The CVD precursor according to claim 20, wherein the aminosilanesource reagent is selected from the group consisting of Si(NMe₂)₃Cl,Si(NEt₂)₂Cl₂, Si(NMe₂)₄, and Si(NEt₂)₄.
 22. The CVD precursorcomposition according to claim 20, wherein R¹ and R² of the aminosilaneare methyl.
 23. The CVD precursor composition according to claim 20,wherein R¹ and R² are ethyl.
 24. The CVD precursor composition accordingto claim 20, wherein R¹ is methyl and R² is ethyl.
 25. The CVD precursorcomposition according to 20, wherein the aminosilane source reagentcompound is selected from the group consisting of: Si(NEt₂)₂Cl₂,Si(NMe₂)₃Cl, Si(NMe₂)₄, Si(NEt₂)₄ and Si(NMeEt)₄.
 26. The CVD precursorcomposition according to claim 20, wherein the precursor compositionfurther comprises a solvent medium selected from the group consistingof: ethers, glymes, tetraglymes, amines, polyamines, alcohols, glycols,aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, cyclicethers and combinations of two or more of the foregoing.
 27. The CVDprecursor composition according to claim 26, wherein the solvent isoctane.
 28. The CVD precursor composition according to claim 20, whereinthe aminosilane source reagent compound is dissolved or suspended in asolvent, wherein the solvent is selected from the group consisting of:ethers, glymes, tetraglymes, amines, polyamines, alcohols, glycols,aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, cyclicethers and combinations of two or more of the foregoing.
 29. The CVDprecursor composition according to claim 20, wherein the aminosilanesource reagent compound is injected by liquid delivery into a chemicalvapor deposition chamber.
 30. The CVD precursor composition according toclaim 20, wherein the aminosilane source reagent compounds is deliveredby bubbler into a chemical vapor deposition chamber.
 31. The CVDprecursor of claim 20, wherein the precursor composition furthercomprises a metalloamide source reagent compound selected from the groupconsisting of:: M(NR¹R²)_(x); and

wherein M is selected from the group consisting of: Zr, Hf, Y, La,Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹ and R²is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6;and
 32. The CVD precursor composition according to claim 31, wherein R¹and R² of the metalloamide source reagent are methyl.
 33. The CVDprecursor composition according to claim 31, wherein R¹ and R² of themetalloamide source reagent compound are ethyl.
 34. The CVD precursorcomposition according to claim 31, wherein R¹ of the metalloamide sourcereagent compound is methyl and R² of the metalloamide source reagentcompound is ethyl.
 35. The CVD precursor composition according to claim31, wherein M is Zr.
 36. The CVD precursor composition according toclaim 31, wherein M is Hf.
 37. The CVD precursor composition accordingto claim 31, wherein the metalloamide source reagent compound isselected from the group consisting of: Zr(NMe₂)₄, Zr(NMeEt)₄, Zr(NEt₂)₄,Ta(NEt₂)₅, Ta(NMe₂)₅, Ta(NMeEt)₅, Zr(NiPr₂)₄, Zr(NMe₂)₂(NPr₂)₂,Zr(NC₆H₁₂)₄, Zr(NEt₂)₂(NPr₂)₂, Hf(NEt₂)₄, Hf(NMe₂)₄, Hf(NMeEt)₄,La(NMe₂)₃, La(NEt₂)₃, La(NMeEt)₃, Al(NMe₂)₃, Al(NEt₂)₃, Y(NMe₂)₃,Y(NEt₂)₃, Y(NMeEt)₃, Ti(NMe₂)₄, Ti(NEt₂)₄, Ti(NMeEt)₄, Ta(NMe₂)₅,Ta(NEt₂)₅.
 38. The CVD precursor composition according to claim 31,wherein the metalloamide source reagent compound is selected from thegroup consisting of Zr(NMe₂)₄, Zr(NEt₂)₄, Zr(NMeEt)₄, Hf(NEt₂)₄,Hf(NMe₂)₄ and Hf(NMeEt)₄.
 39. A CVD precursor composition for forming athin film dielectric on a substrate, such precursor compositionincluding a vapor source reagent mixture including a metalloamide sourcereagent compound selected from the group consisting of: M(NR¹R²)_(x);and

wherein M is selected from the group consisting of: Zr, IIf, Y, La,Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹ and R²is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6.40. The CVD precursor according to claim 39, wherein the CVD precursorcomposition further comprises a vapor source reagent compound selectedfrom the group consisting of: silane, trimethylsilane,tetraethylorthosilicate.
 41. A CVD precursor composition for forming athin film dielectric on a substrate, such precursor compositionincluding a vapor source reagent mixture including a metalloamide sourcereagent compound selected from the group consisting of: M(NR¹R²)_(x);and

wherein M is selected from the group consisting of: Zr, Hf, Y, La,Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹and R²is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6;and an aminosilane source reagent compound selected from the groupconsisting of: H_(x)SiA_(y)(NR¹R²)_(4−x−y); and

wherein H is hydrogen; x is from 0 to 3; Si is silicon; A is a halogen;Y is from 0 to 3; N is nitrogen; each of R¹ and R² is same or differentand is independently selected from the group consisting of H, aryl,perfluoroaryl, C₁-C₈ alkyl, and C₁-C₈ perfluoroalkyl; and n is from 1-6;x is from 0 to 3; Si is silicon; A is a halogen; Y is from 0 to 3; N isnitrogen; n is from 1-6.
 42. A CVD multi-component, single sourcereagent composition useful for forming a silicate thin film dielectricon a substrate, the source reagent composition comprising at least onemetalloamide vapor source reagent compound selected from the groupconsisting of: M(NR¹R²)_(x); and

wherein M is selected from the group consisting of: Zr, Hf, Y, La,Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹ and R²is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6;and an aminosilane source reagent compound selected from the groupconsisting of: H_(x)SiA_(y)(NR¹R²)_(4−x−y); and

wherein H is hydrogen; x is from 0 to 3; Si is silicon; A is a halogen;Y is from 0 to 3; N is nitrogen; each of R¹ and R² is same or differentand is independently selected from the group consisting of H, aryl,perfluoroaryl, C₁-C₈ alkyl, and C₁-C₈perfluoroalkyl; and n is from 1-6;and a solvent medium in which the metalloamide compound and theaminosilane compound are soluble or suspendable.
 43. A CVD method offorming a dielectric thin film on a substrate, comprising the steps of:vaporizing a source reagent composition comprising at least onemetalloamide precursor to form a source reagent precursor vapor;transporting the source reagent precursor vapor into a chemical vapordeposition zone, optionally using a carrier gas; contacting the sourcereagent precursor vapor with a substrate in said chemical vapordeposition zone at elevated temperature to deposit a dielectric thinfilm on the substrate.
 44. The method according to claim 43 wherein themetalloamide precursor is selected from the group consisting of::M(NR¹R²)_(x); and

wherein M is selected from the group consisting of: Zr, Hf, Y, La,Lanthanide series elements, Ta, Ti, Al; N is nitrogen; each of R¹ and R²is same or different and is independently selected from the groupconsisting of H, aryl, perfluoroaryl, C₁-C₈ alkyl, C₁-C₈ perfluoroalkyl,alkylsilyl; and x is the oxidation state on metal M; and n is from 1-6.45. The CVD method according to claim 43, wherein the source reagentcomposition is vaporized in a liquid delivery apparatus.
 46. The CVDmethod according to claim 43, wherein the source reagent vapor istransported into the chemical vapor deposition chamber in a pulseddeposition mode.
 47. The CVD method according to claim 43, wherein thedielectric thin film is deposited in the absence of an oxidizer.
 48. TheCVD method according to claim 43, wherein the source reagent vaporfurther comprises a co-reactive gas.
 49. The CVD method according toclaim 48, wherein the co-reactive gas is selected from the groupconsisting of ozone, water vapor and reactive alcohols.
 50. The CVDmethod according to claim 43, wherein the metalloamide source reagentcompound is selected from the group consisting of: Zr(NMe₂)₄, Zr(NEt₂)₄,Zr(NMeEt)₄, Hf(NMe₂)₄, Hf(NEt₂)₄ and Hf(NMeEt)₄
 51. The CVD methodaccording to claim 42, wherein the metalloamide source reagent compoundis Hf(NMe₂)₄.
 52. The CVD method according to claim 50, wherein themetalloamide source reagent compound is dissolved or suspended inoctane.
 53. The CVD method according to claim 43, wherein themetalloamide source reagent compound is solubilized or suspended in asolvent.
 54. The CVD method according to claim 53, wherein the solventis octane.
 55. The CVD method according to claim 43, wherein themetalloamide source reagent compound is Zr(NMe₂)₄.
 56. The CVD methodaccording to claim 55, wherein the metalloamide precursor furthercomprises La(NMe₂)₃.
 57. The CVD method according to claim 43, whereinthe metalloamide source reagent compound is, Y(NMe₂)₃.
 58. The CVDmethod according to claim 43, wherein the metalloamide source reagentcompound comprises Hf(N(CH₃)₂)₄ and La(N(CH₃)₂)₃.
 59. The CVD methodaccording to claim 43, further comprising an aminosilane precursor. 60.The CVD method according to claim 57, wherein the metalloamide sourcereagent compound is Hf(NMe₂)₄ and the aminosilane source reagentcompound is Si(NMe₂)₃Cl.
 61. The CVD method according to claim 43,wherein the carrier gas is selected from the group consisting of: He,Ar, H₂, N₂ and O₂.
 62. The CVD method according to claim 43, furthercomprising an oxidizing gas selected from the group consisting of: O₂,N₂O, NO and O₃.
 63. The CVD method according to claim 62, wherein theoxidizing gas is N₂O.
 64. The CVD method according to claim 43, furthercomprising an oxidizing gas, wherein the oxidizing gas is N₂O.
 65. TheCVD method according to claim 43, wherein the metalloamide sourcereagent compound is vaporized at temperature in the range of from about100° C. to about 300° C.
 66. The CVD method according to claim 43,wherein the chemical vapor deposition zone is at a temperature in therange of from about 350° C. to about 750° C.